Apparatus for sulfonation of organic compounds



March 17, 1970 J. E. VANDER MEY 3,501,275

. APPARATUS FOR SULFONATION OF URGANIC COMPOUNDS Original Filed Feb. 4} 1964 s Sheets-Sheet 1 INVENTOR JOHN gVANDER MEY ATTORNEY 1 J. E. VANDER MEY 3,501,276

APPARATUS FOR SULFONATION OF ORGANIC COMPOUNDS March 17, 1970 3 Sheets-Sheet 2 Original Filed Feb. 4, 1964 INVENTOR JOHN E.VANDER MEY ATTORNEY March 17, 1970 J. a VANDER MEY APPARATUS FOR SULFONATION OF ORGANIC COMPOUNDS 3 Sheets-Sheet 3 Original Filed Feb. 4, 1964 INVENTOR JOHN EVANDER MEY ATTORNEY United States Patent 3,501,276 APPARATUS FOR SULFONATION OF ORGANIC COMPOUNDS John E. Vander Mey, Cresskill, N.J., assignor to Allied Chemical Corporation, New York, N.Y., a corporation of New York Original application Feb. 4, 1964, Ser. No. 342,485, now Patent No. 3,328,460, dated June 27, 1967. Divided and this application Apr. 12, 1967, Ser. No. 656,609

Int. Cl. B01j 4/ 00, 4/02 US. Cl. 23-284 5 Claims ABSTRACT OF THE DISCLOSURE Apparatus for sulfonation of organic compounds comprising in combination a vertically disposed elongated enclosed reaction chamber, a separating chamber associated with the lower end thereof for separately discharging gas and liquid therefrom, means providing a slot in the upper portion of the reaction chamber Wall extending entirely around the periphery thereof, means for cooling said wall extending entirely around the periphery thereof from and below said slot, means for supplying organic liquid through said slot at a velocity sufficiently low that all of the organic liquid forms a smooth, thin film extending entirely around the periphery of said Wall and descending downwardly in quiescent flow while adhering thereto, and an inlet for a gaseous mixture of inert gas and sulfur trioxide arranged and adapted to discharge a stream of the same downwardly through said reaction chamber around the periphery thereof and in contact with the downwardly flowing film thereon. Preferably, the means for supplying organic liquid comprises an organic liquid supply chamber, disposed above the slot, and an organic supply inlet to the organic liquid chamber which together is adapted to provide the liquid through orifices to the slot at predetermined head uniform throughout slot length and through a laterally extending periphery channel terminating in this slot.

This is a division of application Ser. No. 342,485 filed Feb. 4, 1964, now US. Patent No. 3,328,460.

In recent years, alkyl aromatic sulfonates have received considerable attention principally for their use as synthetic detergents. Among such detergents are certain higher alkyl substituted mononuclear aromatic monosulfonates in which the alkyl groups are predominantly in the range containing from 8 to 20 carbon atoms, many of the more useful alkylates predominating in compounds containing 12 to 14 carbon atoms in the alkyl side chain. These compounds are normally prepared by sulfonation of alkylated mononuclear aromatic compounds commonly referred to as detergent alkylates, among which are the so-called dodecyl benzenes and tridecyl benzenes. In such compounds, the alkyl groups may be of mixed configuration and the products may contain minor proportions of higher and lower alkyl groups. mainly in the 3,501,276 Patented Mar. 17, 1970 tunately, however, the employment of chlorosulfonic acid as the sulfating agent requires removal of by-product hydrochloric acid which is costly and time consuming and moreover, the resulting product is undesirably contaminated with by-product chlorides. The use of sulfuric acid or oleum as the sulfonating agent, suffers from the dis advantage that there is formation of substantial quantities of inorganic salts, e.g., sodium sulfate, which for many purposes are not desirable. For example, in those cases where additives or builders other than sulfates such as phosphates or silicates are desired, it is desirable that the detergent have a low percentage of sodium sulfate and the highest possible percentage of active ingredients.

A method has been proposed to prepare high active materials which involves subjecting the composite material to solvent extraction whereby separation of the sodium sulfate and other inorganic salts is effected by dissolving the active detergent material in the solvent. This procedure is costly since the sodium sulfate is discarded and there is considerable loss of solvent in the process. It has been suggested to produce a high active product by direct reaction of sulfur trioxide with the detergent alkylate. Although this procedure is effective for producing high active products, the reaction with sulfur trioxide is highly exothermic and the product is often oif color. In addition, decomposition of the organic com pound occurs contributing to alkylate losses. For many commercial purposes the off-color product produced is not desirable. For example, in the production of synthetic detergents, the synthetic detergent to be commercially acceptable must for most purposes possess a light color generally about Klett or less (based on a 10% active solution) and contain not more than 5% preferably less than 2% oil (based on active). Various methods have heretofore been proposed to avoid these objectionable eifects resulting from the sulfonation process. In one method, sulfur trioxide was dissolved in an inert solvent and thereafter the reaction was carried out in the diluent medium. This procedure is complicated and expensive since it was found that the solvents utilized were costly to recover and entail losses. More recently, US. Patent 2,923,728 suggests reaction of sulfur trioxide in diluting gas in a circular tube with organic compounds propelled into and through the system by gas.

An object of the present invention is to provide a continuous, efficient, and economical process for the reaction of sulfur trioxide with organic compounds. Another object is to significantly reduce formation of color bodies which normally occur during the sulfonation of organic compounds. Another object is to provide an apparatus for reacting organic compounds continuously with sulfur trioxide. A further object is to provide a new organic feed injection design wherein the organic liquid isinjected into the reaction chamber circumferentially and in contacting relation to the inert gas sulfur trioxide mixture, avoiding formation ofcolor bodiesat the point of contact. These and other objects will become apparent from the following description and accompanying drawings.

In accordance with the present invention, there'is provided an apparatus and process for sulfonating and sulfating an organic liquid by reacting the same with the sulfur trioxide constituent of a gas mixture of inert gas and gaseoussulfur trioxide, the apparatus comprising in combination a vertically disposed elongated enclosed reaction chamber, a separating chamber associated with the lower end thereof for separately discharging gas and liquid therefrom, means providing a slot in the upper portion of the reaction chamber wall extending entirely around the periphery thereof, means for cooling said wall extending entirely around the periphery thereof from and below said slot, means for supplying organic liquid through said slot at velocity sufficiently low that all of the organic liquid forms a smooth, thin film extending entirely around the periphery of said wall and descending downwardly in quiescent flow while adhering thereto, and an inlet for a gaseous mixture of inert gas and sulfur trioxide arranged and adapted to discharge a stream of the same downwardly through said reaction chamber around the periphery thereof and in contact with the downwardly flowing film thereon. The thickness of the film of organic liquid undergoing resulting sulfonatio'n or sulfationis of the order of .002 to .030 inch, preferably .005 to .015 inch. The means for supplying organic liquid preferably comprises an organic liquid supply chamber for the same disposed above the slot and an organic supply inlet to the organic liquid chamber which together is adapted to provide the liquid preferably through metering orifices to the slot at predetermined head uniform throughout slot length and through a laterally extending peripheral channel terminating in the slot.

In a preferred embodiment of the invention, two smooth quiescent flowing films of organic liquid are provided and are contacted while adhering to cooled wall surfaces with sulfur trioxide-air gas mixture passed downwardly between them. In that event, peripheral slots are provided in inner and outer concentric walls defining the reaction chamber, each wall being water jacketed or otherwise suitably exposed to cooling fluid. Supply organic liquid is connected to each of the slots.

The process of the invention comprises providing a stream of organic liquid extending around the entire periphery of the reaction zone, flowing the stream laterally into the reaction zone around its entire periphery as a liquid layer of .002 to .030 inch depth and at velocity not in excess of 30 inches per second, preferably 4 to inches per second as admitted into the reaction zone to form a smooth film of the liquid extending entirely around the periphery of the zone and descending in quiescent flow along the walls thereof, continuously flowing a gaseous stream of sulfur trioxide and inert gas diluent downwardly through the zone in contact with the film, maintaining the contact until reaction between the sulfur trioxide and organic liquid is substantially complete, and cooling the said film through substantially the entire extent of said contact.

The new process is applicable to the sulfation or sulfonation which terms will hereafter be used interchangeably to connote reaction of sulfur trioxide with an organic compound of any of the materials known in the art to be directly sulfatable or sulfonatable by reaction with sulfur trioxide. For example, compounds suitable for sulfation by sulfur trioxide are fatty alcohols, e.g., lauryl, myristyl, and cetyl alcohol, ethoxylated fatty alcohols and ethoxylated alkyl phenols; compounds suitable for sulfonation are olefinic compounds, e.g., aliphatic olefins containing one or more double bonds, such as tetradecene, hexadecene, etc., aromatic hydrocarbons such as those containing a benzene, anthracene, or like structure and alkylated aromatic hydrocarbons such as toluene, ethylbenzene, dodecyl benzene, etc. The advantages of the present method of sulfonation are particularly evident in the production of alkyl aromatic sulfonic acids which when neutralized with a suitable basic reagent such as an alkali metal hydroxide, an amine or an alkanol amine form highly effective detergent compounds. Thus, the process of the present invention will be preferably applied to those alkylated, aromatic compounds in which' the alkyl group or groups contain a total of from 8 to 22 carbon atoms and'in particular, 12 to 14 carbon atoms. In the event that the organic compound is a solid at room temperature, it may be converted to liquid form by any known procedure such as, for example, by preheating the compound. I

The sulfur trioxide used as the active ingredient may be obtained from any suitable source. For example, it may be vaporized from stabilized liquid sulfur trioxide and mixed with air, nitrogen or other inert gas by any suitable known means as, for example, by merging separate streams of sulfur trioxide and diluent inert gas. The sulfur trioxide may be obtained from oleum or may 'be in the form of the well-known converter gas from the contact sulfuric acid process such converter gas being usually an air-sulfur trioxide mixture containing between 6% and about 15% sulfur trioxide. The inert carrier gas in which the vaporized sulfur trioxide is suspended is one which does not react with the sulfonating agent or the sulfonatable organic compound at the specified sulfonation' conditions. Examples of such gases include air, carbon dioxide, carbon monoxide, sulfur dioxide, and nitrogen. Air is preferred because of its availability, low cost and because of the excellent results obtained.

For a clearer understanding of the invention, reference is made to the following drawings in which FIGURE 1 is a side elevation of a preferred embodiment of the assembled apparatus showing the feed injector and reactor section, additional reactor sections and also showing the separator section for separating the sulfated or sulfonated organic compound from spent gas.

FIGURE 2 is a view in section of the feed injector section and part of the top reactor section with apparatus broken away for a better understanding.

FIGURE 3 is a view similar to FIGURE 2 showing the separator section.

FIGURE 4 is a section taken along line 44 of FIG- URE 2.

FIGURE 5 is a front elevation of another embodiment of the invention.

FIGURE 6 is a view in section taken along line 66 of FIGURE 5.

FIGURE 7 is a broken away view of the separator section of the apparatus generally taken along the line 77 of FIGURE 5.

FIGURE 8 is a side view in section of the apparatus shown in FIGURE 7.

FIGURE 9 is a View taken along line 99 of FIG- URE 5.

Referring to FIGURE 1 of the drawings, the reactor designated generally by reference numeral 1 comprises three main sections, a feed injector section 2, a plurality of reactor sections 3, and a separator section 4.

Referring to FIGURES 2 and 4, the reactor section 3, comprises a vertically disposed, vertically elongated casing 5, including an inner reaction wall 6 and an outer reaction wall 7 concentrically disposed within the casing 5 and adapted to form an annular reaction chamber 8 in the space provided between the inner and outer reaction walls.

,The reaction between the sulfonatable organic liquid and the sulfur trioxide takes place on the surface of the inner and outer reaction walls in the reaction chamber and it is highly important that adequate cooling of these walls and the reaction chamber take place during the reaction. For this purpose, there is provided cooling jackets 9 and 11 respectively which extend around the inner and outer walls of the reaction chamber. These cooling jackets are provided with inlet and outlet ports, not shown, which admit and discharge a cooling medium such as water, the cooling medium being circulated through the cooling jackets at a temperature and rate such that the temperature inside the reaction zone is maintained within the range of about 0 to C. during the reaction.

At the upper end of the casing -5 is a flange assembly 12 having an inner component 13, and an outer component 14, the outer component extending outwardly away from the casing as shown in FIGURE 2. Both the inner and outer components of the flange assembly 12 are arranged and adapted so as to form the upper part of the reaction chamber -8 between the outer end of the inner component 13 and the adjacent inner end of the outer component 14.

Referringparticularly to FIGURE 2, the feed injection section 15 includes inner and outer vertically disposed organic liquid feed chambers 16 and 17 concentrically arranged so as to provide a gas inlet passage 18 between the adjacent vertical walls 19 and 21 of the organic feed chambers. The organic liquid to be sulfonated is introduced into the inner and outer feed chambers by means of oil inlet pipes 22 and 23 respectively. Secured to the lower and upper ends of the organic liquid feed chambers are flanges 24 and 25 respectively, flange 24 having inner and outer components 28 and 29 respectively and which are of substantially similar configuration as flange assembly 12. The upper half of the feed injector section 15 is provided with an arc-shaped cylindrical gas inlet tube 31 for receiving the inert gas-S0 gas mixture supplied from an external source. Provision is made for securing gas inlet tube 31 to the external source by means of lip 32 having openings 33 through which bolts or other securing members may be admitted.

The upper half of feed injector section 15, the organic liquid feed chambers 16 and 17, and the reactor section 10, are all secured together by means of threaded bolt 34 and bolts 35, which pass through openings in flanges 12, 24, and 25 and through extension 36 disposed at the lower end of gas inlet conduit 31.

The mixture of inert gas and S0 is introduced into the apparatus through opening 37 of gas inlet conduit 31, which is associated in gas tight relationship with the upper end of gas inlet passage 18.

The sulfonatable organic liquid entering the organic chambers 16 and 17 through oil inlet pipes 22 and 23 is discharged from the chambers 16 and 17 through orifices 38 which are spaced along the inner and outer ends of flange 24 and enter channels 60 peripherally disposed around slots 39 which are located at the inner and outer peripheries of flange components 13 and 14 respectively terminating at their outer ends at the top of reaction chamber 8. The vertical height of each slot can be adi justed by means of shims 41 in recesses 42 which are disposed in concentric relation circumferentially around components 13 and 14 of flange 24. These shims also serve as a seal in that they contain the organic liquid in channels 60. It is understood that the peripheral channels 60 behind the slot may be of the same or different height as slots 39. It is convenient for the fabrication and design that such channels be of the same height as slots 39 as is indicated in the drawings. The organic liquid, entering the reaction chamber 8 through slots 39, is immediately contacted with the inert gas-S0 gas mixture which enters the reaction zone from gas passage 18 and the sulfonation of the organic liquid takes place immediately at the point of contact and as it continues its path along the reactor walls 6 and 7.

Situated at the bottom of the reactor section 3 and attached thereto as shown in FIGURE 1 is separator 43 which separates the spent gas from the sulfated or sulfonated compound. The separator prevents the spent gas from entraining droplets of the liquid product. The design of the separator enables the gas to separate from the organic liquid without breaking through it. This is accomplished by enlarging the cross-sectiona1 area in such a way that the moving organic liquid film is gradually moved out of the path of the spent gas stream producing an increase in the liquid product yield, a cleaner gas stream ready for recycle, and a lighter product. As can .side opposite gas outlet conduit 48 is discharge port 50 which discharges the sulfonated organic compound from the separator. As can be seen from FIGURE 3, the flow of the sulfonated organic compound is directed along the wall of the housing 43 and the inner wall 51 and follows a path to the discharge port 50. At the bottom of the housing is withdrawal conduit 52 which is adapted to remove any entrapped organic compound.

In operation, the sulfonatable organic charge which is preferably dodecyl benzene is fed under pressure into organic liquid supply chambers 16 and .17 through oil inlet pipes 22 and 23 respectively. The pressure and rate of feed of the organic liquid should be such that the liquid present in the chamber is sufficient to maintain channels 60 in liquid flooded condition throughout the operation and to cause the organic liquid to discharge out of the slots onto the reactor walls 6 and 7 at a velocity not in excess of 30 inches per second preferably about 4 to 20 inches per second and differential pressure of about 0 to 5 lbs., preferably substantially zero, i.e., the difference between the pressure at which the organic liquid enters the reaction chamber 8 and the pressure in the reaction chamber is about 0 to 5 lbs., preferably substantially zero.

The liquid dodecyl benzene passes from organic liquid chambers 16 and 17 into channels 60 through orifices 38. Slots 39 may conveniently have a thickness or height of about .002 to .030 inch preferably .005 to .015 inch. This can be regulated by tightening or loosening the bolts 34 and 35. The inert gas which is preferably air and the gaseous sulfur trioxide which may vary from about 2 to 25%, preferably about 5 to 10% sulfur trioxide by volume is introduced into gas inlet conduit 31 through opening 37 to give a gas velocity in the reaction chamber 8 of from about 40 to 300 feet per second, preferably 75 to feet per second. The air-sulfur trioxide mixture passes through gas inlet conduit 31 and into gas passage 18 in a contacting relation with the organic liquid film leaving slots 39. Because of the organic liquid velocity and the pressure difference at which the organic liquid leaves the slots 39 and the pressure in the reaction chamber 8 being substantially zero, the organic liquid discharges out of the slots 39 and immediately turns downward on the reactor walls 6 and 7 without breaking contact or interfering with satisfactory sulfonation. Uneven contact of the organic film with the sulfur trioxide gas mixture tends to promote localized overheating and color bodies form by reason of contact with the stream of sulfur trioxide inert gas, That contact is absolutely uniform throughout the length of the reaction chamber.

As can be seen in FIGURE 2, the cooling of the organic liquid takes place immediately after contacting the air-sulfur trioxide gas mixture and the cooling is continued While a substantial portion of the reaction is taking place. In addition, the organic liquid is also cooled prior to discharge into the reaction chamber by the action of the circulating cooling medium in contact with the lower portions of flange 12. The cooling medium is preferably water which enters cooling jackets 9 and 11 through inlet and outlet ports, not shown. The temperature of the water which circulates through the cooling jacket 9 and 11 maintains the temperature of the reaction which under most conditions is at room temperature. If desired, and depending upon the organic liquid to be sulfonated, additional reactor sections may be added. These additional reactor sections 3, as shown in FIGURE 1, increase the reaction time by increasing the path of the organic liquid. This is particularly advantageous in those reactions where longer contact With air-sulfur trioxide is necessary to produce sufficient sulfonation. Each reactor section is provided with its own cooling means similar to the cooling means of the first reactor section. Thus, the temperature in each reaction zone may be controlled independently, and if desired, the temperature in subsequent stages may be increased for greater activity resulting in substantially complete sulfonation of the organic compound. As will be evident, however, the additional reactor sections are not provided with the particular flange assembly of the top reactor section which includes provision for the particular type of feed injection necessary for the present invention.

47, where it is discharged through gas outlet conduit 48 4 and, if desired, recycled for pickup of additional sulfur trioxide.

In another embodiment of the present invention, details of which are shown in FIGURES 5 through 9, the apparatus features the new horizontal flange injection design as employed with a slot-type reactor.

Referring particularly to FIGURE 5, the reactor designated generally by numeral 54 comprises three main sections, a feed and reactor section 55, a plurality of reactor sections 56 and a separator section 57. These sections are suitably detachably secured together as by bolted flanges 58a.

Referring to FIGURES 6 and 9, the apparatus is provided with a vertically disposed, vertically elongated casing 56a including vertically spaced apart planar side walls 57 of substantial width. Normally, in this type of reactor, the width of the parallel side walls 57 may vary over a wide range depending on the desired commercial output. However, the width is normally from about two inches to as much as 100 inches. These walls are associated at their adjacent vertical edges 58 so as to form vertically elongated reaction chamber 59 as shown in FIGURES 6 and 9 of substantial rectangular slot-like cross section. In general, the distance between the walls of reaction chamber is such that the inert gas-sulfur trioxide mixture is emitted in the form of a sheet-like stream. Communicating with the reaction chamber 59 is gas inlet passage 61 through which the inert gas-sulfur trioxide gas mixture passes after it leaves gas inlet nozzle 61a. Surrounding the gas inlet passage 61 is liquid organic chamber 62 in which the organic liquid is contained after entering through oil inlet pipe 63. Disposed at the bottom of the organic liquid chamber 62 is a flange 64. This flange is rigidly associated with the bottom of the organic liquid chambers and has spaced holes 65 in the flange for discharging the organic liquid into channel 66a thence into slot 66 situated at the top of reaction chamber 59. The slot is formed by the space provided between flanges 64 and 67, the latter being rigidly secured to the upper part of the cooling jacket 68 and being attached to flange 64 by means of bolts 60a. The space between the flanges is provided by means of shims 70 disposed in recesses 80 which surround the gas inlet passage 61. In order to maintain the temperature in the required temperature ranges for effective operation, there is provided cooling jacket 68 which surrounds casing 56 and is of similar configuration therewith. Jacket 68 is provided with inlet port 69 as seen in FIGURE 9, which receives a cooling medium for circulation through the jacket 68 and the cooling medium is discharged through outlet port 71. Situated above gas inlet conduit 61 is gas injection nozzle 61a which receives the inert gas-sulfur trioxide mixture from an outside source. As can be seen from FIGURE 6, the gas injection nozzle has an upper portion of larger crosssectional area than the lower portion. Situation at the bottom of the gas injection nozzle is a flange which is adapted to engage flange 40 disposed at the upper end of the organic chamber. These flanges secure the gas injection nozzle to the top of the organic liquid chambers by means of bolts or other securing members.

Situated at the bottom of the casing 56, and attached thereto is separator 72. As in the first embodiment, the separator is designed to prevent spentgas from entraining droplets of the liquid product and the design of the separator enables the gas to separate from the organic liquid without breaking through it. Referring to FIGURES 7 and 8, the separator comprises a vertically disposed gas escape tube 73 which has an upper portion 74 of larger cross-sectional area than the base of the escape tube. A housing 75 has an upper portion of outwardly flaring walls 76 which extend into cylindrical base 78, the outer walls surrounding at their lower portion, the upper portion of escape tube 73. Situated at the bottom of the cylindrical base 78, extending from the lower portion of tube 73 is outlet conduit 79 which discharges the spent gas mixture. At the bottom of cylindrical base is withdrawal conduit 81 which is adapted to remove organic compound. The organic liquid may be continuously removed as desired through withdrawal conduit 81. The operation of this embodiment of the invention is similar to the operation of the preferred embodiment. The sulfatable organic charge is fed under pressure into liquid supply chamber 62 through oil inlet nozzle 63. The pressure and rate of feed of the organic liquid in the liquid supply chamber 62 should be such as to maintain channel 66a in liquid flooded condition throughout the operation. The liquid dodecyl benzene discharges from the liquid chamber 62 passes into the orifices 65 and thence into the channel 66a terminating at slot 66 disposed circumferentially at the top of the reaction chamber 59. Slot 66 may have the same height as in the first embodiment that is, about .002 to .030 inch preferably .005 to .015 inch. The organic liquid film thickness, the inert gas-sulfur trioxide, and organic velocities are substantially the same as in the first embodiment of this invention.

The organic liquid discharges out of slot 66 in contact with the gas mixture and sulfonation takes place at this point and as the organic liquid continues its path along the reactor walls. The procedure for cooling of the organic liquid and the temperatures employed are substantially the same as in the first embodiment and, if desired, additional reactor sections may be added to the apparatus.

The sulfonated liquid and spent gas leaving the last reactor section enters the separator 72 where the path of the organic liquid is defined by the shape of the walls 76. Referring to FIGURES 7 and 8, the sulfonated organic compound continues to flow along the upper walls 76 away from the path of the spent gas discharging from the separator through discharge port 81. The spent gas, containing trace amounts of the organic compound, enters the separator 72 through opening 82 and is caused to follow the path of escape tube 73 where it is discharged through gas outlet conduit 79 and, if desired, recycled for pickup of additional sulfur trioxide. In addition to the slot-type reactor and the concentric-type tube reactor described in this invention, there may be employed a circular type reactor in combination with the new horizontal flange injection apparatus of the present invention.

The following examples will more fully illustrate the present invention.

EXAMPLE 1 The preferred-apparatus of the present invention was employed and measured approximately 20 feet in length. The apparatus consisted of a feed and reactor section of 6 feet in length and 2 additional reactor sections each measuring 6 feet in length. The separator which was attached to the reactor section was 2 feet in length. Into the feed and reactor section was introduced a mixture of 22.1 pounds per hour of sulfur trioxide diluted with 2340 c.f.h. of recycled air. The air sulfur trioxide.-was then con' tacted with dodecyl benzene fed to the reactor at a rate of about 65 pounds per hour. The dodecyl benzene entered the reaction chamber at a velocity of about 8 inches per secondand at a diflerential pressure of about 1 lb. Cooling water was circulated through the water jackets at about 57 F. and the temperature of the S0 mixture was about 85 F. The operating air pressure was 18.5 p.s.i.g. Theproduct was obtained from the separator at -87 lbs.

per hour for about 99% conversion based on the dodecyl benzene. An analysis of the neutralized product showed a color of 30 based on a 10% solution of the neutralized acid and contained one percent unreacted materialbased on 100% active.

EXAMPLE 2 Utilizing the apparatus of Example 1, the procedure was repeated except that the sulfur trioxide vaporized at the rate of 35.9 pounds per hour was mixed with 3840 cubic feet per hour of recycled air and reacted 'with 105 pounds per hour of dodecyl benzene. The velocity of the dodecyl benzene entering the reaction chamber through the slots was 13 inches per second and entered at a differential pressure of about 1 lb. The operating air pressure was 18.2 p.s.i.g. Cooling water was circulated through the water jackets at about 56 F. and the temperature of the air-S mixture was about 85 F. A ten percent solution of the neutralized acid containing 0.6% unreacted material based on 100% active gave a Klett reading of 50.

EXAMPLE 3 Utilizing the apparatus of Example 1, the procedure was repeated except that the sulfur trioxide vaporized at the rate of 22.3 pounds per hour was mixed with 2406 cubic feet per hour of recycled air and reacted with 65 I In the following example, the reaction chamber was in the form of a round tube and the reactor measured approximately 19 feet in length. The apparatus consisted of a feed and reactor section of 5 feet in length and2 additional reactor sections each measuring 6 feet in'length. The separator which was attached to the reactor section was 2 feet in length. Into the feed and reaction section was introduced a mixture of 11.8 pounds per hour of sulfur trioxide diluted with 1200 c.f.h. of recycled air. The air sulfur trioxide was then contacted with dodecyl benzene fed to the reactor at a rate of about 33.3 pounds per hour. The dodecyl benzene entered the reaction chamber ata velocity of about 6 inchesper second and at a differential pressure of about 1 lb. Cooling water was circulated through the water jacketsat about 44 F. and the temperature of the air-S0 mixture wasabout 82 F. The operating air pressure was 9.6 p.s.i.g. The product was obtained from the separator at 45lbs. per hour for about 99.1% conversion based on the dodecyl benzene. An analysis of the neutralized product showed a color of 30 based on a 10%; solution of the neutralized acid and contained 0.9% unreacted material based on 100% active.

EXAMPLE 5 A reactor having a slot-like reaction chamber was employed for this example. The 'width of the casing was six inches, the thickness of the casing was inchand the T total length, excluding the separator, was 22 feet. The

her at a velocity of about 15 inches per second and at a differential pressure of about 3 lb. Cooling water was circulated through the water jacket at about 52 F. and the temperature of the S0 mixture was about F. The product was obtained from separator at 479 lbs. per hour for about 99.4% conversion based on the dodecyl benzene. An analysis of the neutralized product showed a color of 48 based on a 10% solution of the neutralized acid and contained 0.6% unreacted material based on active.

EXAMPLE 6 Utilizing the apparatus of Example 5, the procedure was repeated except that the sulfur trioxide vaporized at the rate of 91 pounds per hour Was mixed with 10,200 c.f.h. of recycled air and reacted with 272 pounds per hour of dodecyl benzene. The velocity of the dodecyl benzene entering the reaction chamber through the slots was 11 inches per second and entered at a differential pressure of about 1 lb. Cooling water was circulated through the water jacket at about 90 F. and the temperature of the air-S0 gas mixture was F. A ten percent solution of the neutralized acid containing 1.0% unreacted material based on 100% active gave a Klett reading of 48.

Merely as illustrative, the following representative species of organic compounds may be reacted according to the process of the present invention as represented in the preceding examples to give substantially the same results: lauryl, myristyl and cetyl alcohol, tetradecene, hexadecene, toluene and ethylbenzene.

The process and apparatus of the present invention now makes it economically feasible to produce detergent products on a commercial production basis. The concentric tube-type reactor described herein is intended to be used in those cases where huge quantities of sulfonated products are desired: for example, six million pounds or over whereas the slot-type reactor may be employed for quantities up to about three million pounds per year capacity. The color of the finished product is substantially white which is particularly significant in those cases where only a light color detergent product is thought to be desirable because of the association of whiteness with cleanliness. Moreover, there is a low content of oil in the finished product, below 2%, which is particularly significant with respect to yield and purity. In addition, the apparatus of the present invention is particularly economically attractive because of the elimination of moving parts which reduce the chance of breakdown to the very minimum.

Although certain preferred embodiments of the invention have been disclosed for purpose of illustration, it will be evident that various changes'and modifications may be made therein without departing from the scope and spirit of the invention.

I claim:

1. Apparatus for sulfonating a sulfonatable organic compound by reacting the same with the sulfur trioxide constituent of a gas mixture'of inert gas and gaseous sulfur trioxide which comprisesin combination, a vertically disposed elongated enclosed reaction chamber, a separating chamber associated with the lower end thereof for separately discharging gas and liquid therefrom, means providing a slot in the upper portion of the reaction chamber 'wall extending entirely around the peripheryfthereof, a

cooling jacket for cooling said Well extending entirely around the periphery thereof and below said slot, an organic liquid supply chamber disposed above the slot and an organic supply inlet to'the' organic liquid chamber whichtogether is adapted to provide the liquid through orifices to the slot at predetermined head uniform throughout slot length and' through a laterally extending peripheral channel terminating in the slot, said organic liquid being supplied through said slot at velocity sufiiciently low that all of the organic liquid forms a smooth thin film extending entirely around the periphery of said wall and descending downwardly in quiescent flow while adhering thereto, and an inlet for a gaseous mixture of inert gas and sulfur trioxide arranged and adapted to discharge a stream of the same downwardly through said reaction chamber around the periphery thereof and in contact with the downwardly flowing film thereon.

2. Apparatus for sulfonating a sulfonatable organic compound by reacting the same with the sulfur trioxide constituent of a gas mixture of inert gas and gaseous sulfur trioxide which comprises in combination a vertically disposed, vertically elongated casing including an inner and outer reaction wall concentrically disposed within said casing and adapted to form an annular reaction chamber in the space between the inner and outer walls, an inlet for said gas mixture, a cooling jacket enveloping said reaction chamber, a separating chamber associated with said reaction chamber for separately discharging gas and liquid therefrom, vertically disposed organic liquid feed chambers concentrically arranged so as to provide a gas inlet passage from said gas inlet to the upper end of said reaction chamber, said gas inlet passage being disposed between the adjacent vertical walls of the organic feed chambers, a flange disposed at the lower end of said organic feed chamber and a flange assembly including inner and outer components disposed at the upper end of the upper part of said reaction chamber said flange assembly having recesses disposed in concentric relation circumferentially in said inner and outer components, shims, disposed in said recesses, channels circumferentially disposed at the inner and outer peripheries of said inner and outer flange components terminating at their outer ends in slots at the top of said reaction chamber and means for supplying said organic liquid to said channels terminating in said slots.

3. Apparatus for sulfonating a sulfonatable organic compound by reacting the same with the sulfur trioxide constituent of a gas mixture of inert gas and gaseous sulfur trioxide which comprises in combination a vertically disposed, vertically elongated casing including an inner and outer reaction wall concentrically disposed within said casing and adapted to form an annular reaction chamber in the space between the inner and outer walls, an inlet for said gas mixture, a cooling jacket enveloping said reaction chamber, a separating chamber associated with said reaction chamber for separately discharging gas and liquid therefrom, vertically disposed organic liquid feed chambers concentrically arranged so as to provide a gas inlet passage from said gas inlet to the upper end of said reaction chamber, said gas inlet passage being disposed between the adjacent vertical walls of the organic feed chambers, a flange disposed at the lower end of said organic feed chamber and a flange assembly including inner and outer components disposed at the upper end of the upper part of said reaction chamber said flange assembly having recesses disposed in concentric relation circumferentially in said inner and outer components, shims disposed in said recesses, channels circumferentially disposed at the inner and outer peripheries of said inner and outer flange components terminating at their outer ends in slots at the top of said reaction cham-' her said flange having orifices disposed at the lower endof said organic feed chambers, said orifices being spaced along the inner and outer ends of said flange and being adapted to provide a passage for the organic liquid from said organic chambers to said channels terminating in said slots.

4. Apparatus for sulfonating a sulfonatable organic compound by reacting the same with the sulfur trioxide constituent of a gas mixture of inert gas and gaseous sulfur trioxide which comprises in combination a vertically disposed, vertically elongated casing including vertically elongated spaced apart planar side walls of a width, from about 2 inches to inches, said walls being associated at adjacent vertical edges so as to form by the inner surfaces thereof a vertically elongated reaction chamber of substantially rectangular slot-like cross section, a gas injection nozzle for said gas mixture, a cooling jacket enveloping said reaction chamber, a separating chamber associated with said reaction chamber for separately discharging gas and liquid therefrom; a gas inlet passage communicating with said injection nozzle and said reaction chamber, an organic liquid chamber concentrically enveloping said gas inlet passage, a flange disposed at the upper end of the upper part of said reaction chamber, said flange at the upper part of said reaction chamber having a recess surrounding said gas inlet passage, a shim disposed in said recess, a channel circumferentially disposed in said flange terminating at its outer end in a slot at the top of said reaction chamber and means for supplying said organic liquid to said channel terminating in said slot.

5. Apparatus for sulfonating a sulfonatable organic compound by reacting the same with the sulfur trioxide constituent of a gas mixture of inert gas and gaseous su fur trioxide which comprises in combination a vertically disposed, vertically elongated casing including vertically elongated spaced apart planar side walls of substantial width, said walls being associated at adjacent vertical edges so as to form by the inner surfaces thereof a vertically elongated reaction chamber of substantially rectangular slot-like cross section, a gas injection nozzle for said gas mixture, a cooling jacket enveloping said reaction chamber, a separating chamber associated with said reaction chamber for separately discharging gas and liquid therefrom; a gas inlet passage communicating with said injection nozzle and said reaction chamber, an organic liquid chamber concentrically enveloping said gas inlet passage, a flange disposed at the upper end of the upper part of said reaction chamber, said flange at the upper part of said reaction chamber having a recess surrounding said gas inlet passage, a shim disposed in said recess, a

channel circumferentially disposed in said flange terminat-' ing at its outer end in a slot at the top of said reaction chamber, said flange disposed at the lower end of said organic feed chamber having orifices spaced in said flange circumferentially and being adapted to provide a passage for the organic liquid from said organic chamber to said channel terminating in said slot.

References Cited UNITED STATES PATENTS 2,088,027 7/1937 Law et al. 260-459 2,747,794 5/1956 Fegler 23284 2,923,728 2/ 1960 Falk et al. 260-459 3,169,142 2/1965 Knaggs et al. 23284 X FOREIGN PATENTS 243,951 10/ 1959 Australia.

OTHER REFERENCES Trebal, Mass Transfer Operations, McGraw-Hill, p. 50

Cramer et al., Chemical Engineering Practice, vol. 6, pp. 30, 31 (1958).

JOSEPH SCOVRONEK, Primary Examiner D. G. CONLIN, Assistant Examiner US. Cl. X. R. 23285 Patent No. 3,501,276 March 17, 1970 John E. Vander Mey It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as show below:

Column 4, line 52, "surface" should read surfaces Column 7, line 5, "46" should read 48a line 66, "situation" should read situated Column 9, lines 68 and 69, "4,6, 8" should read 4, 8 and 8 Signed and sealed this 29th day of September 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Edward M. Fletcher, Jr.

Commissioner of Patents Attesting Officer 

